COMPUTERIZED SIMULATION OF THERMODYNAMICS FOR MOLTEN LiF-KF SOLUTION BY MONTE CARLO METHOD

The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential energy distribution shows that the average distance be- tween Li^+ and F^- ions will significantly narrow after mixing of molten LiF and KF.This is very similar to the lean-on-one-side effect in molten LiF-KCl solution.The calculated heat of mixing is in fair agreement with the measured one.The dominant source of the energy of mixing may be that the decrease of the repulsion energy between cations,the decrease of the attraction energy between cations and anions,and the decrease of the repulsion energy be- tween anions.

Coherent Application of a Contact Structure to Formulate Classical Non-Equilibrium Thermodynamics

This contribution presents an outline of a new mathematical formulation for Classical Non-Equilibrium Thermodynamics (CNET) based on a contact structure in differential geometry. First a non-equilibrium state space is introduced as the third key element besides the first and second law of thermodynamics. This state space provides the mathematical structure to generalize the Gibbs fundamental relation to non-equilibrium thermodynamics. A unique formulation for the second law of thermodynamics is postulated and it showed how the complying concept for non-equilibrium entropy is retrieved. The foundation of this formulation is a physical quantity, which is in non-equilibrium thermodynamics nowhere equal to zero. This is another perspective compared to the inequality, which is used in most other formulations in the literature. Based on this mathematical framework, it is proven that the thermodynamic potential is defined by the Gibbs free energy. The set of conjugated coordinates in the mathematical structure for the Gibbs fundamental relation will be identified for single component, closed systems. Only in the final section of this contribution will the equilibrium constraint be introduced and applied to obtain some familiar formulations for classical (equilibrium) thermodynamics.

Thermodynamic analysis and simulation for gas baffle entrance collimator of EAST-NBI system based on thermo-fluid coupled method

The world's first full Experimental Advanced Superconducting Tokamak(EAST) is designed with the auxiliary heating method of neutral beam injection(NBI)system. Beam collimators are arranged on both sides of the beam channel for absorbing the divergence beam during the beam transmission process in the EAST-NBI system.The gas baffle entrance collimator(GBEC) is a typical high-heat-flux component located at the entrance of gas baffle. An efficient and accurate analysis of its thermodynamic performance is of great significance to explore the working limit and to ensure safe operation of the system under a high-parameter steady-state condition. Based on the thermo-fluid coupled method, thermodynamic analysis and simulation of GBEC is performed to get the working states and corresponding operating limits at different beam extraction conditions. This study provides a theoretical guidance for the next step to achieve long pulse with highpower experimental operation and has an important reference to ensure the safe operation of the system.

Thermodynamic analysis of combined reforming process using Gibbs energy minimization method: In view of solid carbon formation

Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.

Thermodynamics and kinetics of hydriding and dehydriding reactions in Mg-based hydrogen storage materials

Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.

The thermodynamics analysis and experimental validation for complicated systems in CO_2 hydrogenation process

Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of COhydrogenation is conducted using the Gibbs free energy minimization method.The results show that COreduction to CO needs a high temperature and H/COratio to achieve a high COconversion.However,synthesis of methanol from COneeds a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct COhydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CHfrom COhydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids（HCOOH,CHCOOH and CHCOOH）,propionic acid dominates in the product stream（selectivity above 90%）.The same trend can also be found in the hydrogenation of COto aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of COhydrogenation to alkenes,low temperature,high pressure,and high Hpartial pressure favor the COconversion.CHis the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the COhydrogenation process,which is helpful for the development of high-performance catalysts.

D-Dimensional Dirac Fermions BEC-BCS Crossover Thermodynamics

An effective relativistic continuum massive Proca Lagrangian action is used to account for the Lorentzvector condensation effects on the equation of state of the strongly interacting fermions system.The interior quantumfluctuation effects are incorporated as an external field approximation indirectly through a fictive generalized ThomsonProblem counterterm background.The general analytical formulas for the d-dimensional thermodynamics are given nearthe unitary limit region,In the non-relativistic limit for d=3,the universal dimensionless coefficientε=4/9 andenergy gap △/ε_f=5/18 are reasonably consistent with the existing theoretical and experimental results.In the unitarylimit for d=2 and T=0,the universal coefficient can even approach the extreme occasion ξ=0 corresponding to theinfinite effective fermion mass m~*=∞,which can be mapped to the strongly coupled two-dimensional electrons and isquite similar to the three-dimensional Bose-Einstein condensation of ideal boson gas.Instead,for d=1,the universalcoefficient ξ is negative,implying the non-existence of phase transition from superfluidity to normal state.The solutionsmanifest the quantum Ising universal class characteristic of the strongly coupled unitary fermions gas.

Contribution of biodiversity to ecosystem functioning:a non-equilibrium thermodynamic perspective

Ecosystem stays far from thermodynamic equilibrium. Through the interactions among biotic and abiotic components, and encompassing physical environments, ecosystem forms a dissipative struc- ture that allows it to dissipate energy continuously and thereby remains functional over time. Biotic regulation of energy and material fluxes in and out of the ecosystem allows it to maintain a homeostatic state which corresponds to a self-organized state emerged in a non-equilibrium thermodynamic system. While the associated self-organizational processes approach to homeostatic state, entropy （a measure of irre- versibility） degrades and dissipation of energy increases. We propose here that at a homeostatic state of ecosystem, biodiversity which includes both phenotypic and functional diversity, attains optimal values. As long as biodiversity remains within its optimal range, the corresponding homeostatic state is maintained. However, while embedded environmental conditions fluctuate along the gradient of accelerating changes, phenotypic diversity and functional diversity contribute inversely to the associated self-organizing proc- esses. Furthermore, an increase or decrease in biodiversity outside of its optimal range makes the eco- system vulnerable to transition into a different state.

Thermodynamic stability of interacting fermions system with matrix eigenvalue method

A matrix eigenvalue method is applied to analyse the thermodynamic stability of two-component interacting fermions. The non-relativistic and ultra-relativistic d = 1, 2, 3 dimensions have been discussed in detail, respectively. The corresponding stability region has been given according to the two-body interaction strength and the particle number density ratio.

Non-equilibrium thermodynamic analysis of coupled heat and moisture transfer across a membrane

Non-equilibrium thermodynamics theory is used to analyze the transmembrane heat and moisture transfer process,which can be observed in a membrane-type total heat exchanger(THX).A theoretical model is developed to simulate the coupled heat and mass transfer across a membrane,total coupling equations and the expressions for the four characteristic parameters including the heat transfer coefficient,molardriven heat transfer coefficient,thermal-driven mass transfer coefficient,and mass transfer coefficient are derived and provided,with the Onsager’s reciprocal relation being confirmed to verify the rationality of the model.Calculations are conducted to investigate the effects of the membrane property and air state on the coupling transport process.The results show that the four characteristic parameters directly affect the transmembrane heat and mass fluxes:the heat and mass transfer coefficients are both positive,meaning that the temperature difference has a positive contribution to the heat transfer and the humidity ratio difference has a positive contribution to the mass transfer.The molar-driven heat transfer and thermal-driven mass transfer coefficients are both negative,implying that the humidity ratio difference acts to reduce the heat transfer and the temperature difference works to diminish the mass transfer.The mass transfer affects the heat transfer by 1%–2%while the heat transfer influences the mass transfer by7%–14%.The entropy generation caused by the temperature difference-induced heat transfer is much larger than that by the humidity difference-induced mass transfer.

Non-equilibrium Thermodynamic Analysis of The Transport Properties of Formed-in-Place Zirconium (Ⅳ) Hydrous Oxide-Polyacylate Membranes in aqueous NaNO_3 solution

Nanofiltration of aqueous NaNO3 solution with a dynamically formed Zr(IV) hydrousoxide-PAA membrane is presented. The practical transpoft coefficients Lp, σ, ω were obtainedusing relationships of the non-equilibrium thermodynamics and were used to calculate thefrictional coefficients of a friction model.

Solubility measurement,correlation and thermodynamic properties of 2,3,4-trichloro-1,5-dinitrobenzene in fifteen mono-solvents at temperatures from 278.15 to 323.15 K

The solubility of 2,3,4-trichloro-1,5-dinitrobenzene(TCDNB) was measured by a laser dynamic method over the temperature range from 278.15 K to 323.15 K under 0.1 MPa in fifteen mono-solvents(methanol,ethanol,isopropanol,n-butanol,toluene,dichloromethane,chloroform,tetrachloromethane,1,2-dichloroethane,acetone,ethyl acetate,acetonitrile,N-methylpyrrolidone(NMP),N,Ndimethylformamide dimethyl sulfoxide(DMF),dimethyl sulfoxide(DMSO).The solubility of TCDNB could be increased with increasing temperature in fifteen mono-solvents.TCDNB solubility is in the following order at 298.15 K:NMP>DMF>DMSO>toluene>acetone>ethyl acetate>dichloromethane>1,2-dich loroethane>chloroform>acetonitrile>tetrachloromethane>methanol>ethanol>n-butanol>isopropanol.The KAT-LSER model was used to investigate the solvent effect,which revealed that the hydrogen bond acidity of solvents has a greater effect on TCDNB solubility.The van't Hoff model,the modified Apelblat model,theλh model,and the non-random two liquid(NRTL)model were used to correlate the solubility of TCDNB.The calculated solubility data agreed well with the experimental data,and the modified Apelblat model fit best.Furthermore,the van't Hoff and Gibbs equations were also used to calculate the dissolution thermodynamic properties of TCDNB in various solvents.TCDNB dissolution could be an enthalpy-driven,non-spontaneous,and endothermic process in fifteen mono-solvents.The determination and fitting solubility of TCDNB,as well as the calculation of its thermodynamic properties,would be critical in the purification and crystallization of its preparation process research.

A New Schiff Base Derivatives Designed to Bind Metal Ion (Cu, Co): Thermodynamics and Biological Activity Studies

Schiff base synthesis is usually acid catalyzed and it usually requires refluxing the mixture of aldehydes and amine in ethanolic solution. Synthesis and characterization of Schiff base ligands derived from substituted amine and salicylaldehyde and their complexes (Cu2+, Co2+) are reported. The ligands and ligand-complexes were characterized by melting point, FTIR, CHN-elemental analysis and UV-Visible analysis. The UV-Visible and elemental analysis of complexes established (1:2) mole ratio (M:L). The stability constant and thermodynamic parameters (K, ΔG, ΔH, ΔS) were determined at different temperature (30 - 40)°C which established that the metal-complexes were very stable. The review describes the promising biological activities of Schiff base and their metal complexes.

Study of Thermodynamics of Liquid Noble-Metals Alloys Through a Pseudopotential Theory

The Gibbs-Bogoliubov （GB） inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick （PY） hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree （H）, Taylor （T）, lehimaru-Utsumi （IU）, Farid et al. （F）, and Sarkar et al. （S） is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function.

Mechanism,Kinetics,and Thermodynamic Characteristics for the Demetallization of Used Lubricating Oil via Pyrolysis

This study analyzed the pyrolysis mechanism,developed a pyrolysis kinetic model,and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium alkyl phenolate(T-115B)as a model compound.The pyrolysis process and products were evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Visual inspection indicated that the removal of calcium from T-115B depended primarily on the destruction of micelles caused by the pyrolysis of compounds at high temperatures.The pyrolysis characteristics of T-115B at different heating rates were investigated by thermogravimetry and differential thermal analysis,which revealed two distinct pyrolysis phases.Thus,the pyrolysis mechanism can be described by a twostep model.The activation energy and thermodynamic parameters(ΔH,ΔG,andΔS)were determined by applying the Kissinger-Akahira-Sunose,Flynn-Wall-Ozawa,Friedman,and Starink methods;the average activation energies for T-115B pyrolysis obtained using these methods were 115.80,119.84,124.96,and 116.14 kJ/mol,respectively.Further,both stages of the pyrolysis reaction followed Fn mechanisms with n=1.39 in the first stage and n=0.86 in the second stage.This study provides reliable and effective pyrolysis models along with kinetic and thermodynamic parameters to facilitate the largescale industrial application of used lubricating oil.

基于改进络合铁法的含硫化氢尾气处理工艺模拟与优化

目的有效处理含硫尾气,确保装置“安、稳、长、满、优”运行。方法采用Aspen Plus V11软件基于Peng-Robinson热力学模型对改进络合铁装置的H_(2)S处理过程进行了全流程模拟,并根据Box-Behnken Design对其进行了响应面设计,得到了最佳H_(2)S脱除率及其对应的优化操作参数。结果此模拟流程能够较好地反映改进络合铁装置的实际运行情况,可以作为后续优化研究的基础模型。当循环溶液温度为47.2℃、循环溶液中Fe^(3+)质量分数为8.4100%、循环溶液体积流量为3.12 m^(3)/h、电解槽电压为0.64 V时,改进络合铁装置的H_(2)S脱除率高达99.999988%。此时,外排气中H_(2)S质量浓度为9.5 mg/m^(3),完全可以满足外排气中H_(2)S质量浓度不大于10 mg/m^(3)的约束条件;t检验结果表明,采用响应面法优化得到的预测值和验证值之间不存在显著差异,其准确度一致。结论该研究结果可为进一步提升含H_(2)S尾气处理水平提供准确、可靠的理论支撑和数据来源。

NdF_(3)在LiF熔盐中的溶解及离子结构

LiF-NdF_(3)熔盐体系中离子的构成形式对解析电解钕工艺的电解过程至关重要,本文采用冰点降低法分析LiF-NdF_(3)熔盐体系的离子结构。通过Temkin和Flood模型及热力学计算分析熔盐体系内可能存在的离子团簇,结果表明,NdF_(3)在LiF中的溶解模型符合TemkinⅠ、TemkinⅡ、TemkinⅥ、TemkinⅦ和FloodⅡ、FloodⅥ、FloodⅦ,在LiF-NdF_(3)熔盐体系中主要形成含有1~2个Nd^(3+)的分子团簇,NdF_(3)在LiF内溶解主要形成游离的Nd^(3+)、F-、Li^(+)以及Li^(+)·[NdF_(4)]^(-)、Li^(+)·[Nd2F7]-、2Li^(+)·[Nd_(2)F_(8)]^(2-)分子团簇。

基于间接热力学方法的变换应力方法推导

金属等没有剪胀性的连续材料在根据试验结果建立屈服函数后,可以由Drucker公设及其相关联流动法则推论直接唯一地确定出与屈服函数一致的塑性势函数。但大量试验结果与理论分析都表明Drucker公设对于土材料这种有剪胀性的颗粒材料并不适用,所以更具普适性的热力学成了正确描述土材料塑性流动方向的必要条件。然而塑性流动方向无法只由热力学这一描述材料特性的必要条件唯一地确定,因此便出现了先由试验确定屈服面与塑性流动方向再对其进行热力学验证的间接热力学方法。此外,由于土材料在三维应力空间中不同洛德角对应子午面上的应力应变规律并不一致,因此一般会通过三维化方法来描述土材料在三维应力空间中的力学特性。三维化方法会使得不同子午面上的屈服面及塑性流动方向与三轴压缩状态下所建立的本构模型有所不同,导致三维化后的本构模型是否符合热力学原理成为新的问题。所以本文利用间接热力学方法推导了符合热力学原理的三维化方法,并通过构建变换应力空间将其整理为更有实用性的变换应力方法。

集中供热系统水力热力耦合特性辨识方法研究

集中供热系统的运行能效主要受其水力热力特性的影响,换热站作为连接热源、热网和热用户的枢纽,是分析系统水力热力特性的关键,站内设备的长期运行性能衰减会导致供热系统整体能耗升高、能效下降,因此有必要对站内设备的运行性能进行诊断.基于换热站实测运行数据,分别采用最小二乘法和梯度下降对站内主要设备包括换热器、循环泵和调节阀的性能曲线进行了辨识,从而构建了集中供热系统的水力热力特性计算方法,全面分析了某典型换热站主要设备性能衰减情况和能耗水平,对主要设备运行性能进行了评估,并对设备维护的经济性和碳减排效果进行了计算.结果表明:换热站内主要设备性能存在不同程度衰减,其中换热器传热系数由1.00 kW/(m^(2)·K)下降至0.64 kW/(m^(2)·K),循环泵标况扬程由22.4 m下降至17.3 m,调节阀流通能力由183.0 t/h下降至82.4 t/h,且阀门整体开度较低,以上问题导致了系统整体能耗的增加;为消除气候变化对集中供热系统能耗分析的影响,结合度日数和实际供热面积,对系统能耗进行评价,与标准年相比,测试年采暖季同期平均热耗和电耗分别增加了0.86 GJ/(104 m^(2)·℃·d)和2.38 kW·h/(104 m^(2)·℃·d);对主要设备进行清洗和更换后,集中供热系统采暖季诊断时间内的同期累计电耗可降低16.3%,全生命周期内CO_(2)排放量可减少128.5 t.

基于响应面-遗传算法的文丘里蒸汽疏水阀结构优化设计

为优化文丘里蒸汽疏水阀内件结构,提高其自适应调节性能,以最大疏水范围比为目标,采用Central-Composite响应面设计和遗传算法对文丘里蒸汽疏水阀内件结构进行优化,并对优化前后结构进行分析.结果表明,通过代理模型进行优化设计,大大降低了有限元计算量,提升了优化效率,利用遗传算法得到最佳结构参数为:收缩角为20.8°、喉部长度为4.3mm、扩散角为4.6℃.收缩角、喉部长度和扩散角三个几何参数相互关联,扩散角是影响疏水范围比的最有效参数,其中扩散角对疏水范围比具有负向影响,喉长和收缩角对疏水范围比具有非线性影响,且收缩角对疏水范围比的影响最小.